U.S. patent application number 13/504829 was filed with the patent office on 2012-08-23 for use of fatty acid derivatives in bituminous compositions for improving their resistance to chemical attack and bituminous compositions comprising said derivatives.
This patent application is currently assigned to TOTAL RAFFINAGE MARKETING. Invention is credited to Julien Chaminand, Sylvia Harders.
Application Number | 20120214912 13/504829 |
Document ID | / |
Family ID | 42194746 |
Filed Date | 2012-08-23 |
United States Patent
Application |
20120214912 |
Kind Code |
A1 |
Harders; Sylvia ; et
al. |
August 23, 2012 |
USE OF FATTY ACID DERIVATIVES IN BITUMINOUS COMPOSITIONS FOR
IMPROVING THEIR RESISTANCE TO CHEMICAL ATTACK AND BITUMINOUS
COMPOSITIONS COMPRISING SAID DERIVATIVES
Abstract
The present disclosure relates to the use of at least one fatty
acid derivative of general formula (1) in a bituminous composition
for improving their resistance to aggressive chemical agents, and
in particular to hydrocarbons, such as gasolines, gas oils and/or
kerosenes, general formula (1) being: ##STR00001## with, when n is
equal to 0, an X group chosen from the NH.sub.2 or NHR.sub.3 groups
and when n is equal to 1, an X group which represents the
--NH--(CH.sub.2).sub.m--NH-- group, the R.sub.1, R.sub.2, R.sub.3
groups being, independently of each other, saturated or
unsaturated, linear or branched hydrocarbon groups with 8 to 24
carbon atoms, m being between 1 and 8.
Inventors: |
Harders; Sylvia; (Buchholz,
DE) ; Chaminand; Julien; (Vaulx En Velin,
FR) |
Assignee: |
TOTAL RAFFINAGE MARKETING
Puteaux
FR
|
Family ID: |
42194746 |
Appl. No.: |
13/504829 |
Filed: |
October 29, 2010 |
PCT Filed: |
October 29, 2010 |
PCT NO: |
PCT/IB2010/054916 |
371 Date: |
April 27, 2012 |
Current U.S.
Class: |
524/71 ;
106/284.4 |
Current CPC
Class: |
C08K 3/06 20130101; C08K
5/20 20130101; C08L 95/00 20130101; C08L 53/02 20130101; C08K 5/20
20130101; C08L 95/00 20130101; C08L 91/06 20130101; C08L 91/06
20130101; C08L 95/00 20130101; C08L 2666/02 20130101; C08L 95/00
20130101 |
Class at
Publication: |
524/71 ;
106/284.4 |
International
Class: |
C09D 195/00 20060101
C09D195/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 29, 2009 |
FR |
0957627 |
Claims
1-23. (canceled)
24. A method for improving the resistance of a bituminous
composition to aggressive chemical agents, the method comprising
adding at least one fatty acid derivative in the bituminous
composition wherein the fatty acid derivative has the general
formula (1): ##STR00006## with, when n is equal to 0, an X group
chosen from the NH.sub.2 or NHR.sub.3 groups and when n is equal to
1, an X group which represents the
--NH--(CH.sub.2).sub.m--NH--group, the R.sub.1, R.sub.2, R.sub.3
groups being, independently of each other, saturated or
unsaturated, linear or branched hydrocarbon groups with 8 to 24
carbon atoms, m being comprised between 1 and 8, wherein the
quantity of fatty acid derivative of general formula (1) in the
bituminous composition being comprised between 2% and 6% by mass,
with respect to the mass of the bituminous composition.
25. The method according to claim 24 in which the quantity of fatty
acid derivative of general formula (1) in the bituminous
composition is comprised between 2% and 4% by mass, with respect to
the mass of the bituminous composition.
26. The method according to claim 24 in which the bituminous
composition comprises a polymer.
27. The method according to claim 26 in which the polymer is a
styrene and butadiene copolymer.
28. The method according to claim 27 in which the styrene and
butadiene copolymer has a content of 1,2 double bond units
originating from the butadiene, comprised between 5% and 50% by
mass, with respect to the total mass of the butadiene units.
29. The method according to claim 26 in which the bituminous
composition comprises a cross-linking agent.
30. The method according to claim 24 in which the R.sub.1, R.sub.2,
R.sub.3 groups are, independently of each other, saturated or
unsaturated, linear or branched hydrocarbon groups with 12 to 22
carbon atoms.
31. The method according to claim 24 in which the fatty acid
derivative of general formula (1) is ethylene bis-stearamide.
32. The method according to claim 24 in which the aggressive
chemical agents are hydrocarbons.
33. The method according to claim 24 in which the aggressive
chemical agents are products used for de-icing, defrosting and/or
snow removal and/or compositions based on ethylene glycol and/or
based on propylene glycol.
34. The method according to claim 24 further comprising placing the
bituminous composition in road applications as a surface layer.
35. The method according to claim 24 further comprising mixing the
bituminous composition with aggregates in a bituminous mix.
36. A cross-linked bitumen/polymer composition comprising at least
one bitumen, and at least one fatty acid derivative having the
general formula (1): ##STR00007## with, when n is equal to 0, an X
group chosen from the NH.sub.2 or NHR.sub.3 groups and when n is
equal to 1, an X group which represents the
--NH--(CH.sub.2).sub.m--NH--group, the R.sub.1, R.sub.2, R.sub.3
groups being, independently of each other, saturated or
unsaturated, linear or branched hydrocarbon groups with 8 to 24
carbon atoms, m being comprised between 1 and 8, at least one
cross-linked copolymer of an aromatic monovinyl hydrocarbon and a
conjugated diene, the quantity of fatty acid derivative of general
formula (1) being comprised between 2% and 6% by mass, with respect
to the mass of the cross-linked bitumen/polymer composition, the
quantity of aromatic monovinyl hydrocarbon and conjugated diene,
being comprised between 1% and 10% by mass, with respect to the
mass of the cross-linked bitumen/polymer composition, said
cross-linked bitumen/polymer composition being free of oil of
petroleum origin, oil of vegetable and/or animal origin.
37. The cross-linked bitumen/polymer composition according to claim
36 in which the aromatic monovinyl hydrocarbon and conjugated diene
copolymer has a content of 1,2 double bond units originating from
the conjugated diene, comprised between 5% and 50% by mass, with
respect to the total mass of the conjugated diene.
38. The cross-linked bitumen/polymer composition according to claim
36 comprising a cross-linking agent.
39. The cross-linked bitumen/polymer composition according to claim
36 comprising between 2% and 4% by mass of fatty acid derivative of
general formula (1), with respect to the mass of the cross-linked
bitumen/polymer composition.
40. A cross-linked bitumen/polymer composition according to claim
36 in which the fatty acid derivative of general formula (1) is
ethylene bis- stearamide.
41. The cros-linked bitumen/polymer composition according to claim
36 comprising between 2% and 8% by mass of aromatic monovinyl
hydrocarbon and conjugated diene, copolymer with respect to the
mass of the cross-linked bitumen/polymer composition.
42. A method for preparing a cross-linked bitumen/polymer
composition according to claim 36 in which firstly at least one
bitumen, between 1% and 10% by mass of aromatic monovinyl
hydrocarbon and conjugated diene, and at least one cross-linking
agent are brought into contact between 120.degree. C. and
220.degree. C., for a period of 1 hour to 48 hours, the
cross-linking agent being able to be omitted when the aromatic
monovinyl hydrocarbon and conjugated diene, is the copolymer
according to claim 16, then between 2% and 6% by mass of fatty acid
derivative of general formula (1) is brought into contact between
120.degree. C. and 220.degree. C., for a period of 30 minutes to 48
hours.
43. A bituminous mix comprising the cross-linked bitumen/polymer
composition according to claim 36 in a mixture with aggregates.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a National Phase Entry of International
Application No. PCT/IB2010/054916, filed on Oct. 29, 2010, which
claims priority to French Patent Application Serial No. 09 57 627,
filed on Oct. 29, 2009, both of which are incorporated by reference
herein.
TECHNICAL FIELD
[0002] The present invention relates to the use of additives
derived from fatty acids in bituminous compositions for improving
their resistance to chemical attack. The invention also relates to
the bituminous compositions comprising said additives. The
invention also relates to the method for preparing said bituminous
compositions. The invention finally relates to the mixes comprising
said bituminous compositions and aggregates and their preparation
method.
BACKGROUND
[0003] It is known to use bituminous compositions, in particular
cross-linked bitumen/polymer compositions, as coatings of various
surfaces and, in particular, as road coatings, provided that these
compositions exhibit in combination a certain number of mechanical
characteristics. In order to maintain and/or improve the
characteristics and in particular the mechanical properties of a
conventional bitumen, bituminous compositions have for a long time
been used, in which the bitumen (formed from one or more types of
bitumens) is mixed with one or more functional polymers, in
particular styrene and butadiene elastomers, these elastomers being
optionally chemically cross-linked in situ, optionally using a
coupling or cross-linking agent, for example sulphur or at least
one of its precursors.
[0004] Optimized mechanical characteristics are in particular
crucial for road coating applications. In addition to the
mechanical properties, in the case of bitumens account should be
taken of their susceptibility to certain chemical agents. These
aggressive chemical agents can be, for example hydrocarbon
solvents, in particular petroleum-based solvents such as kerosenes,
gas oils and/or gasolines or also products, in particular fluids,
used for de-icing and/or defrosting and/or snow removal from
aircraft and from taxiing zones. These fluids are for example
aqueous saline solutions of potassium, sodium, magnesium and/or
calcium, and/or compositions based on ethylene glycol and/or based
on propylene glycol.
[0005] The aggressive effect of such chemical agents builds up with
the stresses of intense traffic, in particular of heavy vehicles,
and bad weather, which has the detrimental effect of increasing the
rapid degradation of carriageways, in particular aircraft runways.
This susceptibility of the bitumens to these aggressive chemical
agents, to chemical attack is more particularly problematic for the
bitumens constituting for example tarmacs and the coatings of
airport runways, which are made of bituminous mixes
(bitumen/aggregates conglomerate). In fact, these airport tarmacs
and coatings are frequently soiled by drips of kerosene, during the
filling of aircraft tanks, by leaks or other accidental spills of
petroleum products. Moreover, they are also exposed to the
different fluids used in cold weather to remove ice, frost and/or
snow from aircraft and runways.
[0006] Service stations as well as industrial tank farms can also
be subject to this same problem of the bituminous coatings'
resistance to aggressive chemical agents such as hydrocarbon
solvents and/or de-icing/defrosting/snow removal fluids.
Conventional road carriageways are of course also exposed to this
type of chemical attack.
[0007] In an attempt to remedy this, it has been proposed to
incorporate various additives in bitumens. Thus the patent
EP1311619 describes the use of waxes in bitumens for increasing
their resistance to hydrocarbons. The waxes are in particular
synthetic waxes originating from the Fischer Tropsch synthesis
process. Said bitumens can optionally contain polymers which are
not cross-linked.
[0008] The patent EP1756227 describes bituminous compositions
fluxed using a monoalkyl ester of a vegetable oil or of an animal
oil. The problem of the bituminous compositions' resistance to
chemical attack is not mentioned.
SUMMARY
[0009] The Applicant company was interested in another type of wax
and surprisingly discovered that the selection of a very specific
category of waxes, in a well-defined range of concentration, made
it possible to increase the resistance of the bituminous
compositions and of the cross-linked bitumen/polymer compositions
to chemical attack, to aggressive chemical agents, in particular to
hydrocarbons, such as gasolines, kerosenes and/or gas oils, the
increase in resistance to these chemical agents being even more
pronounced in the case of the cross-linked bitumen/polymer
compositions. Thus the Applicant company noticed that the selection
of fatty acid derivatives, corresponding to general formula (1)
below, in a bituminous composition at a concentration between 2%
and 6% by mass, with respect to the mass of the bituminous
composition, made it possible to increase the resistance of the
bituminous compositions to chemical attack such as that caused by
hydrocarbons such as gasolines, kerosenes and/or gas oils or by
de-icing/defrosting/snow removal products. A synergistic effect was
also observed in the case of a joint use of fatty acid derivatives
of general formula (1) and cross-linked polymer, in particular
styrene and butadiene cross-linked copolymer.
[0010] General formula (1) is as follows:
##STR00002##
with, when n is equal to 0, an X group chosen from the NH.sub.2 or
NHR.sub.3 groups, and when n is equal to 1, an X group which
represents the --NH--(CH.sub.2).sub.m--NH-- group, the R.sub.1,
R.sub.2, R.sub.3 groups being, independently of each other,
saturated or unsaturated, linear or branched hydrocarbon groups
with 8 to 24 carbon atoms, m being comprised between 1 and 8.
BRIEF DESCRIPTION
[0011] The invention relates to the use of at least one fatty acid
derivative in a bituminous composition for improving said
bituminous composition's resistance to aggressive chemical agents,
the fatty acid derivative having as general formula (1):
##STR00003##
[0012] with, when n is equal to 0, an X group chosen from the
NH.sub.2 or NHR.sub.3 groups and when n is equal to 1, an X group
which represents the --NH--(CH.sub.2).sub.m--NH-- group, the
R.sub.1, R.sub.2, R.sub.3 groups being, independently of each
other, saturated or unsaturated, linear or branched hydrocarbon
groups with 8 to 24 carbon atoms, m being comprised between 1 and
8, the quantity of fatty acid derivative of general formula (1) in
the bituminous composition being comprised between 2% and 6% by
mass, with respect to the mass of the bituminous composition.
[0013] Preferably, the quantity of fatty acid derivative of general
formula (1) in the bituminous composition is comprised between 2%
and 4% by mass, with respect to the mass of the bituminous
composition, preferably between 2.5% and 3.5%. Preferably, the
bituminous composition comprises a polymer. Preferably, the polymer
is a styrene and butadiene copolymer.
[0014] Preferably, the styrene and butadiene copolymer has a
content of 1,2 double bond units originating from the butadiene
comprised between 5% and 50% by mass, with respect to the total
mass of the butadiene units, preferably between 10% and 40%, more
preferentially between 15% and 30%, even more preferentially
between 20% and 25%, %, even more preferentially between 18% and
23%. Preferably, the bituminous composition comprises a
cross-linking agent. Preferably, the R.sub.1, R.sub.2, R.sub.3
groups are, independently of each other, saturated or unsaturated,
linear or branched hydrocarbon groups with 12 to 22 carbon atoms,
preferably of 14 to 20 carbon atoms, more preferentially 16 to 18
carbon atoms, even more preferentially 17 carbon atoms.
[0015] Preferably, n is equal to 1. Preferably, m is equal to 2.
Preferably, the fatty acid derivative of general formula (1) is
ethylene bis-stearamide.
[0016] Preferably, the aggressive chemical agents are hydrocarbons,
in particular petroleum hydrocarbons, such as kerosenes, gasolines
and/or gas oils. Preferably, the aggressive chemical agents are
products used for de-icing, defrosting and/or snow removal, such as
saline solutions and/or compositions based on ethylene glycol
and/or based on propylene glycol. Preferably, the bituminous
composition's resistance to aggressive chemical agents is improved
when it is used in road applications as a surface layer.
Preferably, the bituminous composition's resistance to aggressive
chemical agents is improved when it is in a mixture with aggregates
in a bituminous mix.
[0017] The invention also relates to a cross-linked bitumen/polymer
composition comprising at least one bitumen, at least one fatty
acid derivative having the general formula (1):
##STR00004##
[0018] with, when n is equal to 0, an X group chosen from the
NH.sub.2 or NHR.sub.3 groups and when n is equal to 1, an X group
which represents the --NH--(CH.sub.2).sub.m--NH-- group, the
R.sub.1, R.sub.2, R.sub.3 groups being, independently of each
other, saturated or unsaturated, linear or branched hydrocarbon
groups with 8 to 24 carbon atoms, m being comprised between 1 and
8, at least one cross-linked copolymer of an aromatic monovinyl
hydrocarbon and a conjugated diene, preferably of styrene and
butadiene, the quantity of fatty acid derivative of general formula
(1) being comprised between 2% and 6% by mass, with respect to the
mass of the cross-linked bitumen/polymer composition, the quantity
of aromatic monovinyl hydrocarbon and conjugated diene, preferably
styrene and butadiene, copolymer being comprised between 1% and 10%
by mass, with respect to the mass of the cross-linked
bitumen/polymer composition, said cross-linked bitumen/polymer
composition being free of oil of petroleum origin, of oil of
vegetable and/or animal origin.
[0019] Preferably, the aromatic monovinyl hydrocarbon and
conjugated diene, preferably styrene and butadiene, copolymer has a
content of 1,2 double bond units originating from the conjugated
diene, preferably originating from the butadiene, comprised between
5% and 50% by mass, with respect to the total mass of the
conjugated diene units, preferably butadiene, units, preferably
between 10% and 40%, more preferentially between 15% and 30%, even
more preferentially between 20% and 25%, even more preferentially
between 18% and 23%. Preferably, the cross-linked bitumen/polymer
composition comprises a cross-linking agent. Preferably, the
cross-linked bitumen/polymer composition comprises between 2% and
4% by mass of fatty acid derivative of general formula (1), with
respect to the mass of the cross-linked bitumen/polymer
composition, preferably between 2.5% and 3.5%.
[0020] Preferably, the fatty acid derivative of general formula (1)
is ethylene bis-stearamide. Preferably, the cross-linked
bitumen/polymer composition comprises between 2% and 8% by mass of
aromatic monovinyl hydrocarbon and conjugated diene, in particular
styrene and butadiene, copolymer with respect to the mass of the
cross-linked bitumen/polymer composition, preferably between 3% and
7%, more preferentially between 4% and 5%.
[0021] The invention also relates to a method for preparing a
cross-linked bitumen/polymer composition as defined above, in which
firstly at least one bitumen, between 1% and 10% by mass of
aromatic monovinyl hydrocarbon and conjugated diene, preferably
styrene and butadiene copolymer, and at least one cross-linking
agent are brought into contact between 120.degree. C. and
220.degree. C., preferably between 140.degree. C. and 200.degree.
C., more preferentially between 160.degree. C. and 180.degree. C.,
for a period of 1 hour to 48 hours, preferably 4 hours to 24 hours,
more preferentially 8 hours to 16 hours, the cross-linking agent
being able to be omitted when the aromatic monovinyl hydrocarbon
and conjugated diene, preferably styrene and butadiene copolymer is
the copolymer comprising a particular quantity of 1,2 double bond
units originating from the conjugated diene, preferably originating
from the butadiene, then between 2% and 6% by mass of fatty acid
derivative of general formula (1) is brought into contact between
120.degree. C. and 220.degree. C., preferably between 140.degree.
C. and 200.degree. C., more preferentially between 160.degree. C.
and 180.degree. C., for a period of 30 minutes to 48 hours,
preferably 1 hour to 24 hours, more preferentially 4 hours to 16
hours.
[0022] The invention also relates to the use of a bituminous mix
comprising the cross-linked bitumen/polymer composition as defined
above in a mixture with aggregates. The invention also relates to
the method for preparing a bituminous mix as defined above in which
the aggregates and the cross-linked bitumen/polymer composition
according to any one of claims 15 to 20 are mixed between
120.degree. C. and 220.degree. C., preferably between 140.degree.
C. and 200.degree. C., more preferentially between 160.degree. C.
and 180.degree. C.
DETAILED DESCRIPTION
[0023] The additives making it possible to improve the bituminous
compositions' resistance to chemical attack, and in particular to
hydrocarbons, and present in said bituminous compositions according
to the invention, are additives of natural origin, and are in
particular fatty acid derivatives, and in particular amide
derivatives of fatty acids. These additives are represented by
general formula (1) below:
##STR00005##
[0024] with, when n is equal to 0, an X group chosen from the
NH.sub.2 or NHR.sub.3 groups, and when n is equal to 1, an X group
which represents the --NH--(CH.sub.2).sub.m--NH-- group, the
R.sub.1, R.sub.2, R.sub.3 groups being, independently of each
other, saturated or unsaturated, linear or branched hydrocarbon
groups with 8 to 24 carbon atoms, m being comprised between 1 and
8.
[0025] Preferably, the R.sub.1, R.sub.2 and R.sub.3 groups are,
independently of each other, saturated or unsaturated, linear or
branched hydrocarbon groups with 12 to 22 carbon atoms, preferably
14 to 20 carbon atoms, more preferentially 16 to 18 carbon atoms,
even more preferentially 17 carbon atoms. When n is equal to 0, the
additive is chosen from the primary amides of general formula
R.sub.1--CONH.sub.2 (2) or the secondary amides of general formula
R.sub.1--CONH--R.sub.3 (3), the R.sub.1 and R.sub.3 groups being,
independently of each other, saturated or unsaturated, linear or
branched hydrocarbon groups with 8 to 24 carbon atoms, preferably
12 to 22 carbon atoms, more preferentially 14 to 20 carbon atoms,
even more preferentially 16 to 18 carbon atoms, even more
preferentially 17 carbon atoms. Among the primary amides of general
formula R.sub.1--CONH.sub.2 (2), preferably primary amides in which
the R.sub.1 group is a linear or branched, saturated or unsaturated
hydrocarbon group with 8 to 24 carbon atoms, preferably 12 to 22
carbon atoms, more preferentially 14 to 20 carbon atoms, even more
preferentially 16 to 18 carbon atoms, even more preferentially 17
carbon atoms are used.
[0026] There can be mentioned for example erucamide in which
R.sub.1 is a linear and unsaturated hydrocarbon group with 21
carbon atoms of formula CH.sub.3--(CH.sub.2),
--CH.dbd.CH--(CH.sub.2).sub.11--, oleamide in which R.sub.1 is a
linear and unsaturated hydrocarbon group with 17 carbon atoms of
formula CH.sub.3--(CH.sub.2), --CH.dbd.CH--(CH.sub.2).sub.7--,
stearamide in which R.sub.1 is a linear and saturated hydrocarbon
group with 17 carbon atoms of formula
CH.sub.3--(CH.sub.2).sub.16--, docosanamide in which R.sub.1 is a
linear and saturated hydrocarbon group with 21 carbon atoms of
formula CH.sub.3--(CH.sub.2).sub.20--. These primary amides are
commercially available. Among the secondary amides of general
formula R.sub.1--CONH--R.sub.3 (3), secondary amides in which the
R.sub.1 and R.sub.3 groups are, independently of each other,
saturated or unsaturated, linear or branched hydrocarbon groups
with 8 to 24 carbon atoms, preferably 12 to 22 carbon atoms, more
preferentially 14 to 20 carbon atoms, even more preferentially 16
to 18 carbon atoms, even more preferentially 17 carbon atoms are
preferably used.
[0027] There may be mentioned for example oleyl palmitamide in
which R.sub.1 is a linear and saturated hydrocarbon group with 15
carbon atoms of formula CH.sub.3--(CH.sub.2).sub.14--and R.sub.3 is
a linear and unsaturated hydrocarbon group with 18 carbon atoms of
formula CH.sub.3--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.8--,
stearyl erucamide in which R.sub.1 is a linear and unsaturated
hydrocarbon group with 21 carbon atoms of formula
CH.sub.3--(CH.sub.2).sub.7--CH.dbd.CH--(CH.sub.2).sub.11-- and
R.sub.3 is a linear and saturated hydrocarbon group with 18 carbon
atoms of formula CH.sub.3--(CH.sub.2).sub.17--. These secondary
amides are commercially available.
[0028] Preferably, n is equal to 1 and the additive therefore has
the general formula R.sub.1--CO--X--CO--R.sub.2 (4) with X being
the --NH--(CH.sub.2).sub.m--NH--group where m is comprised between
1 and 8, the R.sub.1 and R.sub.2 groups being, independently of
each other, saturated or unsaturated, linear or branched
hydrocarbon groups with 8 to 24 carbon atoms, preferably 12 to 22
carbon atoms, more preferentially 14 to 20 carbon atoms, even more
preferentially 16 to 18 carbon atoms, even more preferentially 17
carbon atoms. The additives of general formula (4) are the
preferred additives.
[0029] Preferably, the R.sub.1 and R.sub.2 groups are,
independently of each other, linear, saturated or unsaturated
hydrocarbon groups comprising 8 to 22 carbon atoms, preferably 12
to 22 carbon atoms, more preferentially 14 to 20 carbon atoms, even
more preferentially 16 to 18 carbon atoms, even more preferentially
17 carbon atoms. Preferably, the R.sub.1 and R.sub.2 groups are,
independently of each other, linear and saturated hydrocarbon
groups comprising 8 to 22 carbon atoms, preferably 12 to 22 carbon
atoms, more preferentially 14 to 20 carbon atoms, even more
preferentially 16 to 18 carbon atoms, even more preferentially 17
carbon atoms. Preferably, m is comprised between 2 and 6, more
preferentially between 3 and 5.
[0030] Preferably, when m is equal to 2, the additive then has the
general formula R.sub.1--CO--NH--(CH.sub.2).sub.2--NH--CO--R.sub.2
(5). In this case the R.sub.1 and R.sub.2 groups, are always,
independently of each other, saturated or unsaturated, linear or
branched hydrocarbon groups with 8 to 24 carbon atoms, preferably
12 to 22 carbon atoms, more preferentially 14 to 20 carbon atoms,
more preferentially 16 to 18 carbon atoms, even more preferentially
17 carbon atoms. The additives of general formula (5) are
particularly preferred additives.
[0031] Preferably, in the general formula
R.sub.1--CO--NH--(CH.sub.2).sub.2--NH--CO--R.sub.2 (5), the R.sub.1
and R.sub.2 groups have the same meaning, which means that the
additive has the general formula
R.sub.1--NH--CO--(CH.sub.2).sub.2--NH--CO--R.sub.1 (6). The
additives of general formula (6) are the more particularly
preferred additives. In this case, R.sub.1 is a linear or branched,
saturated or unsaturated hydrocarbon group with 8 to 24 carbon
atoms, preferably 12 to 22 carbon atoms, more preferentially 14 to
20 carbon atoms, more preferentially 16 to 18 carbon atoms, even
more preferentially 17 carbon atoms. Preferably, R.sub.1 is a
linear, saturated or unsaturated hydrocarbon group with 8 to 24
carbon atoms, preferably 12 to 22 carbon atoms, more preferentially
14 to 20 carbon atoms, more preferentially 16 to 18 carbon atoms,
even more preferentially 17 carbon atoms. Preferably, R.sub.1 is a
linear and saturated hydrocarbon group with 8 to 24 carbon atoms,
preferably 12 to 22 carbon atoms, more preferentially 14 to 20
carbon atoms, more preferentially 16 to 18 carbon atoms, even more
preferentially 17 carbon atoms.
[0032] The preferred additives of general formula (6) are for
example ethylene bis-stearamide with R.sub.1 a linear and saturated
hydrocarbon group with 17 carbon atoms of formula
CH.sub.3--(CH.sub.2).sub.16-- or ethylene bis-oleamide with R.sub.1
a linear and unsaturated hydrocarbon group with 17 carbon atoms of
formula CH.sub.3--(CH.sub.2),--CH.dbd.CH--(CH.sub.2).sub.7--. These
bis-amides are commercially available. Resistance to chemical
attack, in particular resistance to petroleum hydrocarbons such as
gasolines, gas oils and/or kerosenes, is very clearly improved with
ethylene bis-stearamide.
[0033] One of the additives (1) to (6) can be used alone or in a
mixture in the bituminous compositions. The quantity of additives
of general formula (1) to be added to the bituminous compositions
is essential to the invention.
[0034] Thus, the quantity of additives of general formula (1) is
comprised between 2% and 6% by mass, with respect to the mass of
the bituminous composition, preferably between 2% and 4%, more
preferentially between 2.5% and 3.5%, even more preferentially
approximately 3%. The preferred amount of additive of formula (1)
is comprised between 2% and 3,5% by weight en masse, with respect
to the mass of the bituminous composition. The
[0035] Applicant company noticed that a quantity less than 2% by
mass of additives of general formula (1) in the bituminous
composition did not make it possible to improve the bituminous
composition's resistance to chemical attack and in particular to
hydrocarbons. Similarly, a quantity greater than 6% by mass of
additives of general formula (1), even preferably more than 3.5%,
in the bituminous composition, causes a fragility in the bituminous
compositions and in particular in the cross-linked bitumen/polymer
compositions which become brittle. This results in a deterioration
in the elastic recovery, traction and low temperature behaviour
properties, for example with respect to the Fraass point. By
bituminous composition is meant a bituminous composition comprising
bitumen, a bitumen/polymer composition comprising bitumen and a
polymer (physical mixture) or a cross-linked bitumen/polymer
composition comprising bitumen and a cross-linked polymer within
the bitumen.
[0036] The bitumen used can be a bitumen obtained from different
origins. The bitumen which can be used according to the invention
can be chosen from the bitumens of natural origin, such as those
contained in deposits of natural bitumen, natural asphalt or
bituminous sands. The bitumen which can be used according to the
invention can also be a bitumen or a mixture of bitumens
originating from the refining of crude oil such as bitumens from
direct distillation or bitumens from distillation under reduced
pressure or also blown or semi-blown bitumens, residues from
deasphalting with propane or pentane, visbreaking residues, these
different cuts being able to be alone or in a mixture. The bitumens
used can also be bitumens fluxed by adding volatile solvents,
fluxes of petroleum origin, carbochemical fluxes and/or fluxes of
vegetable origin. It is also possible to use synthetic bitumens
also called clear, pigmentable or colourable bitumens. The bitumen
can be a bitumen of naphthenic or paraffinic origin, or a mixture
of these two bitumens.
[0037] The bituminous composition can also comprise at least one
polymer. The polymers which can be used according to the invention
are the polymers which can be used in a standard fashion in the
field of bitumens such as for example the polybutadienes,
polyisoprenes, butyl rubbers, polyacrylates, polymethacrylates,
polychloroprenes, polynorbornenes, polybutenes, polyisobutenes,
polyethylenes, ethylene and vinyl acetate copolymers, ethylene and
methyl acrylate copolymers, ethylene and butyl acrylate copolymers,
ethylene and maleic anhydride copolymers, ethylene and glycidyl
methacrylate copolymers, ethylene and glycidyl acrylate copolymers,
ethylene and propene copolymers, ethylene/propene/diene (EP DM)
terpolymers, acrylonitrile/butadiene/styrene (ABS) terpolymers,
ethylene/acrylate or alkyl methacrylate/glycidyl acrylate or
methacrylate terpolymers and in particular ethylene/methyl
acrylate/glycidyl methacrylate terpolymer and ethylene/alkyl
acrylate or methacrylate/maleic anhydride terpolymers and in
particular ethylene/butyl acrylate/maleic anhydride terpolymer.
[0038] The preferred polymers are copolymers based on conjugated
diene units and aromatic monovinyl hydrocarbon units which can in
particular be cross-linked. The conjugated diene is preferably
chosen from those comprising 4 to 8 carbon atoms, such as 1,3
butadiene (butadiene), 2-methyl-1,3-butadiene (isoprene),
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,2-hexadiene,
chloroprene, carboxylated butadiene and/or carboxylated isoprene.
Preferably, the conjugated diene is butadiene.
[0039] The aromatic monovinyl hydrocarbon is preferably chosen from
styrene, o-methyl styrene, p-methyl styrene, p-tert-butylstyrene,
2,3 dimethyl-styrene, .alpha.-methyl styrene, vinyl naphthalene,
vinyl toluene and/or vinyl xylene. Preferably, the monovinyl
hydrocarbon is styrene. More particularly, the copolymer consists
of one or more copolymers chosen from the aromatic monovinyl
hydrocarbon and conjugated diene, in particular styrene and
butadiene, copolymers, linear or star-shaped, in diblock, triblock
and/or multibranched form, optionally with or without a random
hinge, preferably with a random hinge. Preferably, the copolymer is
an aromatic monovinyl hydrocarbon and conjugated diene diblock
copolymer, in particular a styrene and butadiene diblock copolymer,
in particular a styrene and butadiene diblock copolymer having a
random hinge.
[0040] The aromatic monovinyl hydrocarbon and conjugated diene, in
particular styrene and butadiene, copolymer has an average
molecular mass M.sub.W comprised between 10,000 and 500,000
daltons, preferably between 50,000 and 200,000, more preferentially
between 80,000 and 150,000, even more preferentially between
100,000 and 130,000, even more preferentially between 110,000 and
120,000. The molecular mass of the copolymer is measured by GC
chromatography with a polystyrene standard according to the
standard ASTM D3536.
[0041] The aromatic monovinyl hydrocarbon and conjugated diene, in
particular styrene and butadiene, copolymer advantageously has a
content by weight of aromatic monovinyl hydrocarbon, in particular
of styrene ranging from 5% to 50% by mass, with respect to the mass
of copolymer, preferably from 20% to 40%. The aromatic monovinyl
hydrocarbon and conjugated diene, in particular styrene and
butadiene, copolymer advantageously has a content by weight of
conjugated diene, in particular butadiene, ranging from 50% to 95%
by mass, with respect to the mass of copolymer, preferably from 60%
to 80%.
[0042] Among the conjugated diene units, a distinction is drawn
between the 1,4 double bond units originating from the conjugated
diene and the 1,2 double bond units originating from the conjugated
diene. By 1,4 double bond units originating from the conjugated
diene, is meant the units obtained via a 1,4 addition during the
polymerization of the conjugated diene. By 1,2 double bond units
originating from the conjugated diene, is meant the units obtained
via a 1,2 addition during the polymerization of the conjugated
diene. The result of this 1,2 addition is a so-called "pendant"
vinyl double bond.
[0043] The aromatic monovinyl hydrocarbon and conjugated diene, in
particular styrene and butadiene, copolymer has a content of 1,2
double bond units originating from the conjugated diene, in
particular originating from the butadiene, comprised between 5% and
50% by mass, with respect to the total mass of the conjugated
diene, in particular butadiene, units, preferably between 10% and
40%, more preferentially between 15% and 30%, even more
preferentially between 20% and 25%, even more preferentially
between 18% and 23%. The aromatic monovinyl hydrocarbon and
conjugated diene, in particular styrene and butadiene, copolymer
having a content of 1,2 double bond units originating from the
conjugated diene, in particular originating from the butadiene as
defined above can be used with or without cross-linking agent, as
it has the property of being "self cross-linking", the copolymer
branches are cross-linked, linked to each other via these so-called
"pendant" vinyl double bonds. The bituminous composition comprises
1% to 10% by mass of polymer, in particular aromatic monovinyl
hydrocarbon and conjugated diene, in particular styrene and
butadiene, copolymer, with respect to the mass of the bituminous
composition, preferably 2% to 8%, even more preferentially 3% to
5%.
[0044] The cross-linking of the polymer, in particular of the
aromatic monovinyl hydrocarbon and conjugated diene, in particular
styrene and butadiene, copolymer, in the bituminous composition, is
achieved thanks to the use of a polymer, in particular an aromatic
monovinyl hydrocarbon and conjugated diene, in particular a styrene
and butadiene, copolymer, as defined above and a cross-linking
agent, or thanks to the use of a polymer, in particular an aromatic
monovinyl hydrocarbon and conjugated diene, in particular styrene
and butadiene, copolymer having a particular quantity of 1,2 double
bond units originating from the conjugated diene, in particular
butadiene, this quantity of 1,2 double bond units originating from
the conjugated diene, in particular butadiene, being comprised
between 5% and 50% by mass, with respect to the total mass of the
conjugated diene, in particular butadiene, units preferably between
10% and 40%, more preferentially between 15% and 30%, even more
preferentially between 20% and 25%, even more preferentially
between 18% and 23%, or also thanks to the use of said polymer, in
particular the aromatic monovinyl hydrocarbon and conjugated diene,
in particular styrene and butadiene, copolymer, having the
particular quantity of 1,2 double bond units originating from the
conjugated diene, in particular from the butadiene, in combination
with a cross-linking agent.
[0045] Preferably, the cross-linking agent is chosen from sulphur
and the hydrocarbyl polysulphides, alone or in a mixture,
optionally in the presence of sulphur-donor or non-sulphur-donor
vulcanization accelerators, alone or in a mixture. The sulphur is
in particular flowers of sulphur or also alpha crystallized
sulphur. The hydrocarbyl polysulphides are for example chosen from
the dihexyl disulphides, dioctyl disulphides, didodecyl
disulphides, ditertiododecyl disulphides, dihexadecyl disulphides,
dihexyl trisulphides, dioctyl trisulphides, dinonyl trisulphides,
ditertiododecyl trisulphides, dihexadecyl trisulphides, diphenyl
trisulphides, dibenzyl trisulphides, dihexyl tetrasulphides,
dioctyl tetrasulphides, dinonyl tetrasulphides, ditertiododecyl
tetrasulphides, dihexadecyl tetrasulphides, diphenyl
tetrasulphides, orthotolyl tetrasulphides, dibenzyl tetrasulphides,
dihexyl pentasulphides, dioctyl pentasulphides, dinonyl
pentasulphides, ditertiododecyl pentasulphides, dihexadecyl
pentasulphides, dibenzyl pentasulphides or diallyl pentasulphides.
The sulphur-donor vulcanization accelerators can be chosen from the
thiuram polysulphides, such as for example, the tetrabutylthiuram
disulphides, tetraethylthiuram disulphides and tetramethylthiuram
disulphides, dipentamethylenethiuram disulphides,
dipentamethylenethiuram tetrasulphides or dipentamethylenethiuram
hexasulphides.
[0046] The non-sulphur-donor vulcanization accelerators which can
be used according to the invention can be chosen in particular from
mercaptobenzothiazole and its derivatives, dithiocarbamates and
derivatives, and thiuram monosulphides and derivatives, alone or in
a mixture. There may be mentioned as examples of non-sulphur-donor
vulcanization accelerators, zinc 2-mercaptobenzothiazole, zinc
benzothiazole thiolate, sodium benzothiazole thiolate, benzothiazyl
disulphide, copper benzothiazole thiolate, benzothiazyl
N,N'-diethyl thiocarbamyl sulphide and benzothiazole sulphenamides
such as 2-benzothiazole diethyl sulphenamide, 2-benzothiazole
pentamethylene sulphenamide, 2-benzothiazole cyclohexyl
sulphenamide, N-oxydiethylene 2-benzothiazole sulphenamide,
N-oxydiethylene 2-benzothiazole thiosulphenamide, 2-benzothiazole
dicyclohexyl sulphenamide, 2-benzothiazole diisopropyl
sulphenamide, 2-benzothiazole tertiobutyl sulphenamide, bismuth
dimethyl dithiocarbamate, cadmium diamyl dithiocarbamate, cadmium
diethyl dithiocarbamate, copper dimethyl dithiocarbamate, lead
diamyl dithiocarbamate, lead dimethyl dithiocarbamate, lead
pentamethylene dithiocarbamate, selenium dimethyl dithiocarbamate,
tellurium diethyl dithiocarbamate, zinc diamyl dithiocarbamate,
zinc dibenzyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc
dimethyl dithiocarbamate, zinc dibutyl dithiocarbamate, zinc
pentamethylene dithiocarbamate, dipentamethylene thiuram
monosulphide, tetrabutyl thiuram monosulphide, tetraethyl thiuram
monosulphide and tetramethyl thiuram monosulphide.
[0047] The cross-linking agent can also be chosen from the
compounds of general formula HS--R--SH where R represents a
saturated or unsaturated, linear or branched hydrocarbon group with
2 to 40 carbon atoms, optionally comprising one or more
heteroatoms, such as oxygen. Among the compounds corresponding to
this general formula, there can be mentioned for example 1,2
ethanedithiol, 1,3 propanedithiol, 1,4 butanedithiol, 1,5
pentanedithiol, 1,6 hexanedithiol, 1,7 heptanedithiol, 1,8
octanedithiol, bis-(2-mercaptoethyl)ether,
bis-(3-mercaptoethyl)ether, bis-(4-mercaptoethyl)ether,
(2-mercaptoethyl) (3-mercaptobutyl)ether, (2-mercaptoethyl)
(4-mercaptobutyl)ether, 1,8-dimercapto-3,6-dioxaoctane,
benzene-1,2-dithiol, benzene-1,3dithiol, benzene-1,4-dithiol or
toluene-3,4-dithiol, biphenyl-4,4'-dithiol.
[0048] In general a quantity of cross-linking agent between 0.05%
and 5% by mass, with respect to the mass of the bituminous
composition, preferably between 0.1% and 2%, more preferentially
between 0.2% and 1%, even more preferentially between 0.3% and 0.5%
is used. Preferably, the quantities of polymer and cross-linking
agent are fixed so as to obtain a polymer/cross-linking agent (or
styrene and butadiene copolymer/cross-linking agent) ratio
comprised between 50:1 and 150:1, preferably between 60:1 and
100:1, more preferentially between 70:1 and 80:1.
[0049] The cross-linking of the bituminous compositions can be
demonstrated by carrying out on these bituminous compositions,
tensile tests according to the standard NF EN 13587. The
cross-linked bituminous compositions have a higher tensile strength
than the non-cross-linked bituminous compositions. A higher tensile
strength results in a high ultimate elongation or maximum
elongation (.epsilon. max in %), a high rupture stress or maximum
elongation stress (.sigma. .epsilon. max in MPa), high conventional
energy at 400% (E 400% in J/cm.sup.2) and/or high total energy
(total E in J).
[0050] The bituminous compositions, in particular the cross-linked
bitumen/polymer compositions, have a maximum elongation, according
to the standard NF EN 13587, greater than or equal to 400%,
preferably greater than or equal to 500%, more preferentially
greater than or equal to 600%, even more preferentially greater
than or equal to 700%. The bituminous compositions, in particular
the cross-linked bitumen/polymer compositions, have a maximum
elongation stress, according to the standard NF EN 13587, greater
than or equal to 0.4 MPa, preferably greater than or equal to 0.6
MPa, more preferentially greater than or equal to 0.8 MPa, even
more preferentially greater than or equal to 1.2 MPa. The
bituminous compositions, in particular the cross-linked
bitumen/polymer compositions, have a conventional energy at 400%,
according to the standard NF EN 13587, greater than or equal to 3
J/cm.sup.2, preferably greater than or equal to 5 J/cm.sup.2, more
preferentially greater than or equal to 10 J/cm.sup.2, even more
preferentially greater than or equal to 15 J/cm.sup.2. The
bituminous compositions, in particular the cross-linked
bitumen/polymer compositions, have a total energy, according to the
standard NF EN 13587, greater than or equal to 1 J, preferably
greater than or equal to 2 J, more preferentially greater than or
equal to 4 J, even more preferentially greater than or equal to 5
J.
[0051] The bituminous composition can also optionally comprise
adhesiveness additives and/or surfactants. They are chosen from the
alkyl amine derivatives, alkyl polyamine derivatives, alkyl
amidopolyamine derivatives, alkyl amidopolyamine derivatives and
quaternary ammonium salt derivatives, alone or in a mixture. The
most used are the tallow propylene-diamines, tallow amido-amines,
quaternary ammoniums obtained by quaternization of tallow
propylene-diamines, tallow propylene-polyamines. The quantity of
adhesiveness additives and/or surfactants in the bituminous
composition according to the invention is comprised between 0.1%
and 2% by mass, with respect to the mass of the bituminous
composition, preferably between 0.2% and 1.degree. /o.
[0052] The bituminous composition, in particular the cross-linked
bitumen/polymer composition according to the invention is free of
oil of petroleum origin, oil of vegetable origin and/or animal
origin as the presence of an oil could alter the bituminous
composition's, in particular the cross-linked bitumen/polymer
composition's properties of resistance to chemical attack, and in
particular to hydrocarbons in the bituminous composition, in
particular the cross-linked bitumen/polymer composition by
softening the bituminous composition, in particular the
cross-linked bitumen/polymer composition too much.
[0053] The bituminous composition is prepared by mixing the
additive of general formula (1) with the bituminous composition at
a temperature of 120.degree. C. to 220.degree. C., preferably
140.degree. C. to 200.degree. C., more preferentially 160.degree.
C. to 180.degree. C., for a duration of 30 minutes to 48 hours,
preferably 1 hour to 24 hours, more preferentially 2 hours to 16
hours, even more preferentially 4 hours to 8 hours. For the
preparation of the cross-linked bitumen/polymer composition, first
of all the cross-linked bitumen/polymer composition is prepared
without the additive of general formula (1), by mixing the bitumen,
the polymer, in particular the aromatic monovinyl hydrocarbon and
conjugated diene copolymer, in particular the styrene and butadiene
copolymer, and optionally the cross-linking agent at a temperature
of 120.degree. C. to 220.degree. C., preferably 140.degree. C. to
200.degree. C., more preferentially 160.degree. C. to 180.degree.
C., for a duration of 1 hour to 48 hours, preferably 4 hours to 24
hours, more preferentially 8 hours to 16 hours.
[0054] When the bitumen/polymer composition is cross-linked, the
additive of general formula (1) is then added to the cross-linked
bitumen/polymer composition at a temperature of 120.degree. C. to
220.degree. C., preferably 140.degree. C. to 200.degree. C., more
preferentially 160.degree. C. to 180.degree. C., for a duration of
30 minutes to 48 hours, preferably 1 hour to 24 hours, more
preferentially 2 hours to 16 hours, even more preferentially 4
hours to 8 hours. The bituminous compositions and the cross-linked
bitumen/polymer compositions comprising the additive of general
formula (1) are essentially intended for producing bituminous mixes
or surface dressings for road applications.
[0055] In the case of the bituminous mixes, bituminous compositions
and cross-linked bitumen/polymer compositions comprising the
additive of general formula (1) are mixed with aggregates in order
to provide bituminous mixes which are resistant to chemical attack,
in particular resistant to hydrocarbons. The quantity of bituminous
composition comprising the additive of general formula (1) in the
bituminous mix is comprised between 1 and 10% by mass, with respect
to the mass of bituminous mix, preferably between 2 and 8%, more
preferentially between 3 and 5%, the remainder being constituted by
the aggregates.
[0056] The bituminous mixes are used as a surface layer in zones
where the surface can come into contact with aggressive chemical
agents such as petroleum hydrocarbons or de-icing, defrosting
and/or snow removal products, for example, by way of run-offs. Such
surfaces include for example car parks, airport tarmacs and
runways, service stations, roundabouts, tank farms.
[0057] The additive of general formula (1) is used for improving
the bituminous compositions' resistance to chemical attack caused
by hydrocarbons, in particular petroleum hydrocarbons such as
gasolines, fuels, premium fuels, kerosenes, jet fuels, gas oils,
diesels. Similarly the additive of general formula (1) is used for
improving the bituminous compositions' resistance to chemical
attack caused by the de-icing, defrosting and/or snow removal
products such as the aqueous saline solutions of potassium, sodium,
magnesium and/or calcium, and/or compositions based on ethylene
glycol and/or based on propylene glycol. The additive of general
formula (1) is particularly effective for improving the bituminous
compositions' resistance to hydrocarbons, in particular to
petroleum hydrocarbons such as gasolines, kerosenes and/or gas
oils.
EXAMPLES
[0058] The bituminous compositions' resistance to hydrocarbons is
evaluated according to an internal method similar to the method
used for measuring the Ring and Ball temperature of bitumens (EN
1427). The rings filled with bituminous compositions are placed in
the supports conventionally used in the EN 1427 method, 5 g balls
are placed on these supports. The supports are placed in a beaker
filled with kerosene, instead of the water conventionally used in
the standard EN 1427 method. The bituminous compositions'
resistance to kerosene is evaluated at ambient temperature and
under stirring. The duration, softening time of the two bituminous
disks is evaluated until each ball, covered with bituminous
compositions, moves downwards by (25.0.+-.0.4) mm. The problem
arises of the dissolution of the bituminous compositions in
kerosene. The liquid in the beaker then becomes opaque, and it is
impossible to know visually when the balls drop. We carried out an
inspection by taking the supports out at regular time
intervals.
[0059] Different bituminous compositions are prepared from: [0060]
bitumen of penetrability equal to 41 1/10 mm and with a Ring and
Ball temperature equal to 51.8.degree. C., [0061] styrene and
butadiene diblock copolymer comprising 25% by mass of styrene, with
respect to the mass of the copolymer, and 12% 1,2 double bond units
originating from the butadiene, with respect to the mass of
butadiene and a molecular mass Mw of 115,000 daltons, [0062]
flowers of sulphur, [0063] an additive of general formula (1) in
which n is equal to 1, m is equal to 2, R.sub.1 and R.sub.2 are
identical and are linear and saturated hydrocarbon groups with 17
carbon atoms (ethylene bis-stearamide), in the quantities in %
indicated in Table I below.
TABLE-US-00001 [0063] TABLE I Bituminous compositions C.sub.1
C.sub.2 C.sub.3 C.sub.4 C.sub.5 C.sub.6 C.sub.7 C.sub.8 Bitumen 100
99 98 97 95.9 94.9 93.9 92.9 SB Copolymer -- -- -- -- 4 4 4 4
Sulphur -- -- -- -- 0.1 0.1 0.1 0.1 Ethylene -- 1 2 3 -- 1 2 3
bis-stearamide
[0064] The bituminous compositions are prepared as follows: For the
bituminous compositions C.sub.2 to C.sub.4, a bitumen is introduced
into a reactor maintained at 185.degree. C. under stirring at 300
rpm. The content of the reactor is maintained at 185.degree. C.
under stirring at 300 rpm for 10 minutes. The additive of general
formula (1) is then introduced into the reactor. The content of the
reactor is maintained at 185.degree. C. under stirring at 300 rpm
for 1 hour.
[0065] For the cross-linked bitumen/polymer composition C.sub.5,
the bitumen and the styrene/butadiene SB copolymer is introduced
into a reactor maintained at 185.degree. C. and under stirring at
300 rpm. The content of the reactor is then maintained at
185.degree. C. under stirring at 300 rpm for 4 hours. Flowers of
sulphur are then introduced into the reactor. The content of the
reactor is maintained at 185.degree. C. under stirring at 300 rpm
for 2 hours, then at 185.degree. C. and under stirring at 150 rpm
for 12 hours. For the cross-linked bitumen/polymer compositions
C.sub.6 to C.sub.8, the same procedure is followed and the additive
of general formula (1) is then introduced into the reactor. The
content of the reactor is maintained at 185.degree. C. under
stirring at 300 rpm for 1 hour.
[0066] The compositions C.sub.2 to C.sub.4 correspond to bituminous
compositions constituted by bitumen and an additive according to
general formula (1). The bituminous composition C.sub.1 is a
control bituminous composition comprising bitumen alone, and no
additive according to general formula (1). The bituminous
composition C.sub.2 is a control bituminous composition comprising
only 1% by mass of additive according to general formula (1). The
bituminous compositions C.sub.3 and C.sub.4 are bituminous
compositions according to the invention comprising 2% or 3% by mass
of additive according to general formula (1).
[0067] The compositions C.sub.6 to C.sub.8 correspond to c linked
bitumen/polymer compositions constituted by bitumen, an additive
according to general formula (1) and a cross-linked styrene and
butadiene copolymer. The bituminous composition C.sub.5 is a
control cross-inked bitumen/polymer composition comprising no
additive according to general formula (1). The cross-linked
bitumen/polymer composition C.sub.6 is a control composition
comprising only 1% by mass of additive of general formula (1). The
cross-inked bitumen/polymer compositions C.sub.7 and C.sub.8 are
cross-linked bitumen/polymer compositions according to the
invention comprising 2% or 3% by mass of additive according to
general formula (1).
[0068] For the bitumen/polymer compositions C.sub.1, to C.sub.8,
the following characteristics are determined:
[0069] .sup.(1) penetrability at 25.degree. C. denoted P.sub.25 (
1/10mm) measured according to the standard EN 1426,
[0070] .sup.(2) Ring and Ball temperature denoted RBT (.degree. C.)
measured according to the standard EN 1427,
[0071] .sup.(3) Pfeiffer index denoted PI defined by the formula
below:
PI = 1952 - 500 .times. log ( P 25 ) - 20 .times. RBT 50 .times.
log ( P 25 ) - RBT - 120 ##EQU00001##
[0072] .sup.(4) elastic recovery denoted ER (%) measured at
25.degree. C. according to the standard NF EN 13398,
[0073] .sup.(5) the time necessary for the ball to move down
(25.0.+-.0.4) mm,
[0074] The results are given in Table II below:
TABLE-US-00002 TABLE II Bituminous compositions C.sub.1 C.sub.2
C.sub.3 C.sub.4 C.sub.5 C.sub.6 C.sub.7 C.sub.8 P.sub.25 41 35 29
25.2 28.4 23.3 26 25.7 (1/10 mm) RBT (.degree. C.) 51.8 62 83 100.5
74.0 74.0 86.4 97.0 PI -1.19 0.57 3.38 5.04 2.09 1.68 3.56 4.72 ER
(%) -- -- -- -- 82 80 69 57 Time 30 40 7 h 11 h 1 h 1 h 10 h 18 h
min min 30 30
[0075] It is noted that the resistance to kerosene of the
bituminous compositions C.sub.3 and C.sub.4 is very clearly
improved when 2% or 3% by mass of additive of general formula (1)
is added to the bituminous composition C.sub.1. The resistance to
kerosene is 7 hours for the bituminous composition C.sub.3 and 11
hours for the bituminous composition C.sub.4 whereas it is only 40
minutes for the bituminous composition C.sub.2 comprising 1% by
mass of additive of general formula (1).
[0076] It is also noted that the resistance to kerosene of the
cross-linked bitumen/polymer compositions C.sub.7 and C.sub.8 is
very clearly improved when 2% or 3% by mass of additive of general
formula (1) is added to the cross-linked bitumen/polymer
composition C.sub.5. The resistance to kerosene is 18 hours for the
cross-linked bitumen/polymer composition C.sub.8 and 10 hours for
the cross-linked bitumen/polymer composition C.sub.7, whereas it is
only 1 hour and 30 minutes for the cross-linked bitumen/polymer
composition C.sub.6 comprising 1% by mass of additive of general
formula (1). Hydrocarbon resistance tests are also carried out on
bituminous mixes according to the standard EN12697-43.
[0077] The bituminous mixes E.sub.1, E.sub.4, E.sub.5 and E.sub.8
comprise respectively 5.6% by mass of bituminous composition
C.sub.1, C.sub.4, C.sub.5 or C.sub.8, with respect to the mass of
the bituminous mix, and 94.4% by mass of aggregates (composition of
the aggregates: 38% by mass of 6/10 aggregates, with respect to the
mass of the aggregates, 5% by mass of 4/6 aggregates, 5% by mass of
2/4 aggregates, 48% by mass of 0/2 sand and 4% by mass of fillers,
content of spaces 8.5-9.5%). The mixes are prepared by mixing the
bituminous compositions and aggregates at 180.degree. C.
[0078] The tests are carried out according to the standard
EN12697-43 in gas oil and kerosene. The results are given in Table
III below:
TABLE-US-00003 TABLE III Bituminous mixes E.sub.1 E.sub.4 E.sub.5
E.sub.8 Resistance to gas oil 24 h (A/B) 5/4 1/2 3/3 1/3 Resistance
to gas oil 72 h (A/B) -- 1/5 4/7 1/5 Resistance to kerosene 13/11
2/4 6/5 1/4 24 h (A/B) Resistance to kerosene -- 1/10 9/10 3/8 72 h
(A/B)
[0079] It is noted that the bituminous mix E4 is more resistant to
gas oil and kerosene than the bituminous mix E.sub.1, all the A and
B values of the bituminous mix E.sub.4 being less than those of the
bituminous mix E.sub.1. The addition of 3% by mass of additive of
general formula (1) in pure bitumen has therefore very clearly
improved the resistance of the pure bitumen to gas oil and
kerosene.
[0080] It is noted that the bituminous mix E.sub.8 is more
resistant to gas oil and kerosene than the bituminous mix E.sub.5,
all the A and B values of the bituminous mix E.sub.6 being less
than or equal to those of the bituminous mix E.sub.5. The addition
of 3% by mass of additive of general formula (1) to a cross-linked
bitumen/polymer composition has therefore improved the resistance
of the cross-linked bitumen/polymer composition to gas oil and
kerosene.
* * * * *